Radiation curable compositions containing vinyl ether functionality and methods for their preparation

ABSTRACT

The present invention relates to radiation curable silicone vinyl ethers and methods for preparing silicone vinyl ethers. More particularly, the present invention relates compositions containing vinyl ether functional silicones and to the preparation and use of silicone vinyl ethers which are curable by addition of photocleavable acids and exposure to ultraviolet or electron beam radiation.

This application is a division of application Ser. No. 08/443,521 filedMay 18, 1995, now U.S. Pat. No. 5,629,095, issued May 13, 1997.

BACKGROUND OF THE INVENTION

The present invention relates to radiation curable silicone vinyl ethersand methods for preparing silicone vinyl ethers. More particularly, thepresent invention relates to compositions containing vinyl etherfunctional silicones and to the preparation and use of silicone vinylethers which are curable by addition of photocleavable acids andexposure to actinic radiation.

Alkenyl ether functional organosilicon compounds have been described inthe art. For example, U.S. Pat. No. 4,617,238 to Crivello discloses andclaims a photopolymerizable composition comprising (a) anorganopolysiloxane having at least one Si-bonded vinyloxy functionalgroup of the formula H₂ C═CH--O--G--, where G is alkylene (such aspropylene) or alkylene interrupted by at least one divalentheteroradical selected from --O--, divalent phenylene, or substituteddivalent phenylene, or combination of such heteroradicals, and (b) anonium salt catalyst. The U.S. Pat. No. '238 patent also describes amethod wherein the vinyl ether group is introduced into theorganopolysiloxane by addition (hydrosilylation) of compounds with anallyl and a vinyl ether group to an SiH group of the organopolysiloxanein the presence of a platinum catalyst. In the method of the U.S. Pat.No. '238, only the allyl group is added to the SiH group while the vinylether group is preserved and thus only one vinyl ether group for eachSiH group can be incorporated into the siloxane molecule at any giventime.

U.S. Pat. No. 4,707,503 to Itoh et al. discloses unsaturatedorganopolysiloxanes containing at least two organosiloxane groupsrepresented by the formula ##STR1## wherein R1 is a divalent hydrocarbongroup, R² is a hydrogen atom or a methyl group, R³ is a substituted orunsubstituted monovalent hydrocarbon group, X is a group --O--(CH₂)₂S--, and m is a number of 0, 1, or 2.

U.S. Pat. No. 5,057,549 to Herzig et al. discloses alkenyloxy functionalorganosilicon compounds which contain at least one Si-bonded Y radicalper molecule having the formula --(CH₂)₂ --R² --(A--R³)_(z)--O--CH═CH-CH₂ --R⁴, wherein A denotes --O--, --S--, or --C(O)O--, R²denotes a linear or branched alkylene radical having from 1 to 7 carbonatoms per radical or cycloalkylene radical having from 5 to 7 carbonatoms per radical, R³ denotes a linear or branched alkylene radicalhaving from 2 to 4 carbon atoms per radical, which may be substituted bya hydroxyl group, methoxy group, ethoxy group, or trimethylsiloxy group,R⁴ denotes a hydrogen atom or an alkyl radical having from 1 to 4 carbonatoms per radical, and z has a value of 0, 1, or 2. Thealkenyloxy-functional organopolysiloxanes can be crosslinked for examplewith ultraviolet light and can be used for preparing coatings. The U.S.Pat. No. '549 further discloses that the alkenyloxy functionalorganosilicon compounds are prepared by reacting compounds of theformula CH₂ ═CH--R² --(AR³)_(z) --OCH₂ --CH═CH--R⁴ with an organosiliconcompound having at least one Si-bonded hydrogen atom in the presence ofa hydrosilylation catalyst, followed by a second step which effects thetransfer of the carbon-carbon double bond to the carbon bonds beside theether oxygen.

European Patent Publication No. 0462389 teaches thermosettingorganopolysiloxanes with oxyalkylene vinyl ether groups bonded by SiOCgroups and the vinyl groups may be substituted by alkyl radicals.EPO'389 also teaches a method for the preparation of these compounds andtheir application as photochemically thermosetting polysiloxanes inencapsulating compounds, as nonstick coating compounds for flat carriersor as modified additives in compounds which can be thermoset radically,cationically or by UV or electron radiation.

Another vinyl ether functional silicone is described in U.S. Pat. No.5,039,716 to Vara et al. which discloses alk-1-enyl ether silicateshaving the formula X!_(4-n) Si OR¹ OCH═CH--R² !_(n) wherein X is ahalogen or --OR wherein R is lower alkyl or a mixture of halogen and OR,a mixture of OR and hydrogen or a mixture of halogen and hydrogen, R¹contains from 1 to 8 carbon atoms and is alkylene, alkenylene,alkynylene, optionally alkoxylated with up to 20 units of ##STR2##wherein Y is hydrogen or methyl and R² is each hydrogen or lower alkyland n has a value of 1 to 4. The U.S. Pat. No. '716 also discloses aprocess for preparing vinyl ether silicates.

The methods described hereinabove which rely on competition between thevinyl ether group and other alkenyl groups on the same compound do notresult in conversion of SiH to vinyl ether. In contrast, the method ofthe present invention results in the quantitative conversion ofsiloxanes to vinyl ether, the preferred radiation sensitive group.

SUMMARY OF THE INVENTION

In accordance with the present invention a novel process for preparingsilicone vinyl ethers has been discovered. The present invention furtherrelates to novel silicone vinyl ether compounds.

The present invention relates to a method of making a vinyletherfunctional siloxane, the method comprising the steps of: (I) reacting(a) a silane having the formula R_(x) Si(OR¹)_(4-x) ; (b) water; and (c)an acidic condensation catalyst, wherein R is a monovalent hydrocarbonor halohydrocarbon radical having from 1 to 20 carbon atoms, R¹ is amonovalent alkyl radical having from 1 to 8 carbon atoms, x has a valueof from 0 to 3, with the proviso that the molar ratio of water to alkoxyradicals is less than 0.5; (II) removing alcohol from the mixture ofstep (I); (III) neutralizing the mixture of step (II); (IV) adding avinyl ether compound having the formula HOR² OCH═CH₂ wherein R² is adivalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms to the mixture of step (III); (V) adding atransesterification catalyst to the mixture of step (IV); and (VI)removing volatiles from the mixture of step (V).

The present invention also relates to an alternative method of making avinylether functional siloxane, the method comprising the steps of: (I)reacting in the presence of a non-acidic equilibration catalyst (a) acyclic compound having the formula ##STR3## and (b) a compound havingthe formula HOR¹ OCH═CH₂, wherein R is a monovalent hydrocarbon radicalor halohydrocarbon radical having from 1 to 20 carbon atoms, R¹ is adivalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, and x has a value of from 3 to 10; (II) removing volatilesfrom the mixture of step (I); and (III) neutralizing the mixture of step(II). The present invention further relates to novel vinyletherfunctional polysiloxane compounds. The present invention further relatesto a curable composition comprising the novel vinylether functionalpolysiloxane compound hereinabove in combination with a photocleavableacid. This invention also relates to a method of making a curablecomposition, the method comprising the steps of (I) applying the curablecomposition to a solid substrate to form a coating; and (II) exposingthe coating to an energy source selected from the group consisting of(i) actinic radiation and (ii) actinic radiation in combination withheat in an amount sufficient to cure the coating. It is an object of thepresent invention to provide a novel method of preparing vinyl etherfunctional siloxanes.

It is another object of the present invention to provide a novel methodof preparing UV or EB curable organopolysiloxanes suitable for pressuresensitive adhesive release applications.

It is a further object of this invention to provide novel silicone vinylether compounds.

It is also an object of the present invention to produce silicone vinylether copolymers or oligomers which are curable by addition ofphotocleavable acids and exposure to UV (ultraviolet) or EB (electronbeam) radiation.

It is a further object of this invention to provide UV-curable siliconecompositions which may be catalyzed by a variety of curing catalysts.

It is a further object of this invention to provide novel UV curablevinyloxy polysiloxane compositions having especially rapid cure rates.

These and other features, objects, and advantages of the presentinvention will be apparent upon consideration of the following detaileddescription of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Thus the present invention relates to a method comprising the steps of(I) reacting (a) a silane having the formula R_(x) Si(OR¹)_(4-x), (b)water, and (c) an acidic condensation catalyst, wherein R is amonovalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, R¹ is a monovalent alkyl radical having from 1 to 8 carbonatoms, x has a value of from 0 to 3, with the proviso that the molarratio of water to alkoxy radicals is less than 0.5, (II) removingalcohol from the mixture of step (I), (III) neutralizing the mixture ofstep (II), (IV) adding a vinyl ether compound having the formula HOR²OCH═CH₂ wherein R² is a divalent hydrocarbon or halohydrocarbon radicalhaving from 1 to 20 carbon atoms to the mixture of step (III); (V)adding a transesterification catalyst to the mixture of step (IV); and(VI) removing volatiles from the mixture of step (V).

Step (I) in the method of the present invention comprises reacting asilane having the formula R_(x) Si(OR¹)_(4-x) with water and an acidiccondensation catalyst. The silane in the method of the present inventionis a silane having the formula R_(x) Si(OR¹)_(4-x) wherein R is amonovalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, R¹ is a monovalent alkyl radical having from 1 to 8 carbonatoms, and x has a value from 0 to 3. It is also required in the methodof this invention that the molar ratio of water to alkoxy radicals isless than 0.5.

In the formula shown immediately above each R denotes a monovalenthydrocarbon radical having from 1 to 20 carbon atoms. Monovalenthydrocarbon radicals include alkyl radicals, such as methyl, ethyl,propyl, butyl, hexyl, and octyl; cycloaliphatic radicals, such ascyclohexyl; aryl radicals, such as phenyl, tolyl, and xylyl; aralkylradicals, such as benzyl and phenylethyl; and olefinic hydrocarbonradicals, such as vinyl, allyl, methallyl, butenyl, and hexenyl,octenyl, cyclohexenyl and styryl. Alkenyl radicals are preferablyterminally unsaturated. Highly preferred monovalent hydrocarbon radicalfor the silane in the method of this invention are methyl, phenyl,vinyl, and 5-hexenyl. Monovalent halohydrocarbon radicals free ofaliphatic unsaturation include any monovalent hydrocarbon radical notedabove which has at least one of its hydrogen atoms replaced with ahalogen, such as fluorine, chlorine, or bromine. Preferred monovalenthalohydrocarbon radicals have the formula C_(n) F_(2n+1) CH₂ CH₂ --wherein the subscript n has a value of from 1 to 8, such as, forexample, CF₃ CH₂ CH₂ -- and C₄ F₉ CH₂ CH₂ --. The several R radicals canbe identical or different, as desired. R¹ in the method of the presentinvention is a monovalent alkyl radical having from 1 to 8 carbon atomswhich include alkyl radicals such as methyl, ethyl, propyl, butyl,hexyl, and octyl. The amount of silane employed in the method of thepresent invention varies depending on the amount of water andcondensation catalyst employed. It is preferred for purposes of thisinvention that from 50 to 99 weight percent of silane be used, and it ishighly preferred that from 85 to 95 weight percent of silane beemployed, said weight percent being based on the total weight of thecomposition.

Water is also included in the mixture of step (I), preferably clearwater, and most preferably distilled and/or deionized water. It ispreferred for purposes of this invention that from 1 to 50 weightpercent of water be used, and it is highly preferred that from 5 to 15weight percent of water be employed, said weight percent being based onthe total weight of the composition.

The acidic condensation catalysts suitable for use in Step (I) of thisinvention include condensation catalysts having a pH of less than 7.Examples of the acidic condensation catalysts suitable for thecondensation reaction in the method of the present invention include butare not limited to hydrochloric acid (HCl), H₂ SO₄ sulfonic acids, H₃PO₄, (PNCl₂)_(x), acid anhydrides, acid clays, ion exchange resins,RCOCl, and (RCO)₂ O, wherein R is a monovalent hydrocarbon orhalohydrocarbon radical having from 1 to 20 carbon atoms such as methyl.It is preferred for purposes of this invention that the condensationcatalyst is selected from the group consisting of hydrochloric acid, H₂SO₄, and sulfonic acids. The amount of acidic condensation catalystneeded for the method of the present will be determined by the skilledartisan through routine experimentation. Typically, this component isemployed at a level of about 0.1 to about 5 weight percent, preferably0.1 to 1 weight percent, said weight percent being based on the totalweight of the composition.

As stated hereinabove, it is required in the method of this inventionthat the molar ratio of water to alkoxy radicals is less than 0.5. It ishighly preferred that this molar ratio be from 0.1 to 0.4.

Step (II) in the method of the present invention comprises removingalcohol from the reaction mixture of step (I). Methods of removingvolatile components are well known in the art and need no extensivedelineation herein. Any method of removing volatile components can beused in the present invention, such methods exemplified by, but notlimited to, heating and/or application of a vacuum, molecular stills,rotoevaporators, and wipe film evaporators, with the preferred methodbeing wipe film evaporators. It is preferred in the method of thepresent invention that the alcohol in Step (I) be removed by heating themixture to a temperature of above 80° C.

Step (III) in the method of the present invention comprises neutralizingthe mixture of step (II). Neutralization of acidic mixtures is wellknown in the art and needs no extensive delineation herein. It ispreferred in the method of the present invention that the mixture ofstep (II) be neutralized by adding a basic compound to it such as sodiumbicarbonate (NaHCO₃), calcium carbonate (CaCO₃), Na₂ CO₃, (NH₄)₂ CO₃,CO₂, H₂ O, and a filter aid such as diatomaceous earth.

Step (IV) in the method of the present invention comprises adding avinyl ether compound having the formula HOR² OCH═CH₂ wherein R² is adivalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms to the neutralized mixture of step (III).

In the formula immediately above R² is a divalent hydrocarbon orhalohydrocarbon radical having from 1 to 20 carbon atoms. Divalenthydrocarbon radicals suitable as R² are exemplified by alkyleneradicals, such as methylene, ethylene, trimethylene,2-methyltrimethylene, pentamethylene, hexamethylene,3-ethyl-hexamethylene, octamethylene, --CH₂ (CH₃)CH--, --(CH₂)₄ --,--CH₂ CH(CH₃)CH₂ --, and --(CH₂)₁₈ --; cycloalkylene radicals such ascyclohexylene; arylene radicals such as phenylene, and combinations ofdivalent hydrocarbon radicals such as benzylene, i.e. --C₆ H₄ CH₂ --.

Examples of suitable divalent halohydrocarbon radicals include anydivalent hydrocarbon radical wherein one or more hydrogen atoms havebeen replaced by halogen, such as fluorine, chlorine or bromine.Preferably divalent halohydrocarbon radicals have the formula --CH₂ CH₂C_(n) F_(2n) CH₂ CH₂ -- wherein n has a value of from 1 to 10 such asfor example --CH₂ CH₂ CF₂ CF₂ CH₂ CH₂ --. Preferably R² in is analkylene radical having from 1 to 8 carbon atoms such as methylene,ethylene, propylene, butylene, hexylene, and cyclohexyldimethylene.

The amount of vinyl ether compound employed in the method of the presentinvention varies depending on the amount of silane, water andcondensation catalyst employed. It is preferred for purposes of thisinvention that from 5 to 90 weight percent of vinyl ether be used, andit is highly preferred that from 15 to 50 weight percent of vinyl etherbe employed, said weight percent being based on the total weight of thecomposition.

Step (V) in the method of the present invention comprises adding atransesterification catalyst to the mixture of step (IV). Suitabletransesterification catalysts have been described for example in U.S.Pat. No. 3,133,111 which is incorporated herein by reference and havebeen described in other publications and include alkali metal alkoxides,Sn compounds, Ti compounds, Ba compounds, as well as standard strongalkali compounds. Strong acid compounds are to be avoided as they tendto polymerize oxyalkenyl groups. Examples of suitabletransesterification catalysts include dimethyltin neodecanoate,dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate,dibutyltin dioctoate, zinc napthenate, cobalt napthenate, zinc octylate,tin octylate, cobalt octylate, diisooctyl mercaptoacetate, zirconiumnapthenate, zirconium octylate, tetrabutyl orthotitanate, tetraisopropyltitanate, barium hydroxide monohydrate, stannous octoate, and otherorganic metal catalysts. It is preferred for purposes of this inventionthat the transesterification catalyst be selected from alkali metalalkoxides such as tetraisopropyl titanate, barium hydroxide monohydrate,and sodium methoxide. The amount of catalyst needed for the method ofthe present will be determined by the skilled artisan through routineexperimentation. Typically, this component is employed at a level ofabout 0.1 to about 5 weight percent, preferably 0.1 to 3 weight percent,said weight percent being based on the total weight of the composition.

Step (VI) in the method of the present invention comprises removingvolatiles from the mixture of Step (V). Methods of removing volatilecomponents are well known in the art and need no extensive delineationherein. Any method of removing volatile components can be used in thepresent invention, such methods exemplified by, but not limited to,molecular stills, rotoevaporators, and wipe film evaporators, with thepreferred method being wipe film evaporators.

The method of the present invention can further comprise heating themixture after step (I). By heat it is meant infrared radiation, hot-air,microwave radiation, etc. It is preferred for the method of the presentinvention that the mixture resulting from Step (I) be heated from roomtemperature to a temperature of less than about 150° C., and it ishighly preferred that the mixture resulting from step (I) be heated at atemperature of from 50° to 85° C.

The method of the present invention can further comprise adding apolydiorganosiloxane. The polydiorganosiloxane preferably is a compoundhaving the formula HOSiR³ ₂ O(R³ ₂ SiO)_(n) SiR³ ₂ OH wherein R³ isselected from the group consisting of a monovalent hydrocarbon orhalohydrocarbon radical having from 1 to 20 carbon atoms and hydrogen,and n has a value from 0 to 15,000. The monovalent hydrocarbon andhalohydrocarbon radicals suitable as R³ in the method of this inventionare as delineated above for R in Step (I). It is preferable that thepolyorganosiloxane be added prior to Step (IV).

In a preferred embodiment of the present invention, thepolydiorganosiloxane is a hydroxyl-endblocked polydimethylsiloxanehaving the formula HOMe₂ SiO(Me₂ SiO)_(n) SiMe₂ OH wherein n has a valueof from 10 to 60.

The polyorganosiloxanes are well known in the silicone art and needs nodetailed delineation herein. Suitable hydroxyl-endblockedpolydiorganosiloxanes are disclosed for example, in U.S. Pat. Nos.2,807,601,; 2,985,545; 3,900,617; 4,190,688; 4,293,671; 4,476,241;4,559,396; 4,562,096; 4,587,136 and 4,609,574 which are included hereinby reference to further delineate hydroxyl end-blockedpolydiorganosiloxanes and how to make them. It is preferable that about10 to 80 weight percent of hydoxyl-endblocked polydiorganosiloxane beemployed in the method of this, invention. It is highly preferred forpurposes of the present invention that 25 to 50 weight percent ofhydroxyl-endblocked polydiorganosiloxane be employed, said weightpercent being based on the total weight of the composition.

The method of the present invention can further comprise adding analcohol having the formula R⁴ OH, wherein R⁴ is is a monovalenthydrocarbon or halohydrocarbon radical having from 1 to 20 carbon atoms.The monovalent hydrocarbon and halohydrocarbon radicals suitable as R⁴in the method of this invention are as delineated above for R in Step(I). It is preferred in the process of the instant invention that thealcohol be added after step (I). It is preferable that about 1 to 50weight percent of alcohol be used in the instant method and it is highlypreferred for purposes of the present invention that 10 to 30 weightpercent of alcohol be used, said weight percent being based on the totalweight of the composition.

The present invention further relates to an alternative method of makinga vinylether functional siloxane, the method comprising the steps of:(I) reacting: (a) a silane having the formula R_(x) Si(OR¹)_(4-x) ; (b)water; (c) a non-acidic condensation catalyst; and (d) a vinyl ethercompound having the formula HOR² OCH=CH₂ wherein R is a monovalenthydrocarbon or halohydrocarbon radical having from 1 to 20 carbon atoms,R¹ is a monovalent alkyl radical having from 1 to 8 carbon atoms, R² isa divalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms x has a value of from 0 to 3, with the proviso that themolar ratio of water to alkoxy radicals is less than 0.5; (II) removingalcohol from the mixture of step (I); (III) neutralizing the mixture of(II); (IV) adding a transesterification catalyst to the mixture of(III); and (V) removing volatiles from the mixture of step (IV).

In this alternative method the silane, water, vinyl ether compound ofstep (I) are as delineated above for the method of making the vinyletherfunctional siloxanes of the present invention, including amounts andpreferred examples thereof. Steps (II) through (V) in the instantalternative method are also as delineated above for the method of makingthe vinylether functional siloxanes of the present invention, includingamounts and preferred examples thereof.

The non-acidic condensation catalysts suitable for use in Step (I) ofthis invention include basic and neutral condensation catalysts, orthose having a pH of 7 or a pH of greater than 7. Examples of thenon-acidic condensation catalysts suitable for the condensation reactionin this method of the present invention include neutral condensationcatalysts such as heat, amine carboxylates, heavy metals carboxylates,isocyanates. Also suitable for the non-acidic condensation catalyst inthis method of the invention are basic condensation catalysts such assilanolates, phenoxides, mercaptides, CaO, BaO, LiOH, BuLi, amines,ammonium hydroxides. It it preferred for purposes of this invention thatthe non-acidic condensation catalyst is selected from the groupconsisting of silanolates and ammonium hydroxides.

The amount of non-acidic condensation catalyst needed for the method ofthe present invention will be determined by the skilled artisan throughroutine experimentation. Typically, this component is employed at alevel of about 0.001 to about 0.5 weight percent, preferably 0.02 to 0.2weight percent, said weight percent being based on the total weight ofthe composition.

The instant method can further comprise adding an endcapping agent priorto step (III). Preferably the endcapping agent is a compound having theformula R³ ₃ SiQSiR³ ₃, wherein R³ is a monovalent hydrocarbon radicalor halohydrocarbon radical having from 1 to 20 and Q is a heteroradicalselected from the group consisting of oxygen, and nitrogen. Themonovalent hydrocarbon and halohydrocarbon radicals suitable as R³ inthis method of the invention are as delineated in the methods delineatedabove including preferred embodiments thereof. Preferred endcappingagents for the instant method also include compounds which contain--SiMe₃ groups or --SiMe₂ R groups wherein R is a group selected fromphenyl, vinyl, hexenyl, trifluoropropyl, and hydroxyl, but are notlimited thereto. Especially preferred endcapping agents for this methodof the invention include hexamethyldisilazane, hexamethyldisiloxane, Me₃SiO(Me₂ SiO)₂ SiMe₃, XMe₂ SiO(Me₂ SiO)₂ SiMe₂ X, wherein X is selectedfrom the group consisting of vinyl, phenyl, trifluoropropyl, hexenyl,and a halogen.

The amount of endcapping agent needed for the method of the presentinvention will be determined by the skilled artisan through routineexperimentation. Typically, this component is employed at a level ofabout 25 to about 75 weight percent, preferably 40 to 60 weight percent,said weight percent being based on the total weight of the composition.

The method of the present invention can further comprise heating themixture after step (I). Heating in this method of the invention is asdelineated in the method above including preferred temperatures andmethods of applying heat.

The method of the present invention can further comprise adding apolydiorganosiloxane prior to step (III). The polydiorganosiloxane ispreferably a hydroxyl-endblocked polydiorganosiloxane and is asdelineated in the method above including amounts and preferredembodiments thereof.

The present invention also relates to an additional method of making avinylether functional siloxane, the method comprising the steps of: (I)reacting in the presence of a non-acidic equilibration catalyst (a) acyclic compound having the formula ##STR4## and (b) a compound havingthe formula HOR⁶ OCH═CH₂ wherein R⁵ is a monovalent hydrocarbon radicalor halohydrocarbon radical having from 1 to 20 carbon atoms, R⁶ is adivalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, and y has a value of from 3 to 10, (II) removing volatilesfrom the mixture of (I); and (III) neutralizing the mixture of (II).

Step (I) in this method of the invention comprises reacting (a) a cycliccompound having the formula ##STR5## and (b) a compound having theformula HOR⁶ OCH═CH₂ wherein R⁵ is a monovalent hydrocarbon radical orhalohydrocarbon radical having from 1 to 20 carbon atoms, R⁶ is adivalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, and y has a value of from 3 to 10 in the presence of anon-acidic equilibration catalyst. The monovalent hydrocarbon andhalohydrocarbon radicals of R⁵ are as delineated above in the othermethods of this invention including amounts and preferred embodimentsthereof. The divalent hydrocarbon or halohydrocarbon radicals of R⁶ arealso as delineated above in the other methods of this inventionincluding amounts and preferred embodiments thereof.

Suitable non-acidic equilibration catalysts for this method of theinvention include catalysts such as heat, amine carboxylates, heavymetals carboxylates, isocyanates. Also suitable for the non-acidicequilibration catalyst in this method of the invention are catalystssuch as silanolates, phenoxides, mercaptides, CaO, BaO, LiOH, BuLi, andamines, potassium hydroxides, cesium hydroxides, ammonium hydroxides,and phosphorus hydroxides. It is preferred for purposes of thisinvention that the non-acidic equilibration catalyst is selected fromthe group consisting of silanolates and ammonium hydroxides. It ispreferred that the silanolates are selected from potassium silanolatesand sodium silanolates. The amount of non-acidic equilibration catalystneeded for this method of the invention will be determined by theskilled artisan through routine experimentation. Typically, thiscomponent is employed at a level of about 0.1 to about 5 weight percent,preferably 0.1 to 3 weight percent, said weight percent being based onthe total weight of the composition.

Step (II) in this method of the invention comprises removing volatilesfrom the mixture of step (I). Methods of removing volatile componentsare as delineated in the methods above including preferred methodsthereof.

Step (III) in the method of the present invention comprises neutralizingthe mixture of step (II). Methods of neutralizing mixtures are asdelineated above including preferred method thereof. It is preferredhowever in this method that the mixture of step (III) be neutralized byadding carbon dioxide or acetic acid followed by filtration to removesalt by-products.

This method of the present invention can further comprise heating themixture after step (I). Heating in this method of the invention is asdelineated in the methods above including preferred temperatures andmethods of applying heat.

The method of the present invention can further comprise adding apolydiorganosiloxane prior to step (III). The polydiorganosiloxane ispreferably a hydroxyl-endblocked polydiorganosiloxane and is asdelineated in the methods above including amounts and preferredembodiments thereof.

The method of this invention can further comprise adding a silane havingthe formula R⁷ _(a) Si(OR⁸)_(4-c) prior to Step (III). In the formulaabove R⁷ is a monovalent hydrocarbon or halohydrocarbon radical havingfrom 1 to 20 carbon atoms, R⁸ is a monovalent alkyl radical having from1 to 8 carbon atoms, and c has a value from 0 to 3. The silane in thismethod of the invention is as delineated above for the silane in theother methods of this invention including amounts and preferredembodiments thereof.

The present invention further relates to a random siloxane copolymercomposition having the general formula: ##STR6## wherein R is amonovalent hydrocarbon radical or halohydrocarbon radical having from 1to 20 carbon atoms, R¹ is a monovalent hydrocarbon or halohydrocarbonradical having from 1 to 8 carbon atoms, or is a compound having theformula R² OCH═CH₂ wherein R² is a divalent hydrocarbon orhalohydrocarbon radical having from 1 to 20 carbon atoms, w has a molepercent of from greater than 0 to 100, x has a mole percent of from 0 toless than 100, y has a mole percent of from 0 to less than 100, z has amole percent of from 0 to less than 100, a is an integer of from 0 to 3,b is an integer of from 0 to 2, the sum of w+x+y+z being equal to 100mole percent, with the proviso that at least one R² OCH═CH₂ group existsin each molecule.

The siloxane copolymer of the present invention thus is comprised ofsiloxane units of the formula ##STR7## siloxane units of the formula##STR8## siloxane units of the formula (RSiO_(3/2))_(y), and siloxaneunits of the formula (SiO₂)_(z) with the molar ratios defined in theformula hereinabove.

The monovalent hydrocarbon and halohydrocarbon radicals and the divalenthydrocarbon or halohydrocarbon radicals in the siloxane polymer of theinstant invention are as delineated above in the methods of thisinvention including preferred embodiments thereof. It is preferred inthe instant invention that w has a mole percent of from 5 to 90, x has amole percent of from 0 to 75, y has a mole percent of from 0 to 40, andz has a mole percent of from 0 to 10. It is further preferred that themolecular weight of said composition be controlled to deliver asolvent-free viscosity of from 20 cps to 2000 cps at 22° C.

The present invention is further directed to a curable coatingcomposition comprising (A) the siloxane copolymer delineated above and(B) a photocleavable acid. Suitable photocleavable acids for thecompositions of the present invention include onium salts and certainnitrobenzyl sulfonate esters. Preferred for the compositions of thisinvention are onium salts having the formulae R₂ I⁺ MX_(n) ⁻, R₃ S⁺MX_(n) ⁻, R₃ Se⁻ MX_(n) ⁻, R₄ P⁺ MX_(n) ⁻, and R₄ N⁺ MX_(n) ⁻, wherein Ris the same or different organic radicals having from 1 to 30 carbonatoms, including aromatic carbocyclic radicals of from 6 to 20 carbonatoms which can be substituted with from 1 to 4 monovalent hydrocarbonradicals selected from alkoxy radicals having from 1 to 8 carbon atoms,alkyl radicals having from 1 to 8 carbon atoms, nitro, chloro, bromo,cyano, carboxy, mercapto, and aromatic heterocyclic radicals includingpyridyl, thiophenyl, pyranyl, etc. The symbol M in the formulaehereinabove are metals or metalloids which include transition metalssuch as such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs,rare earth metals such as the lanthanides, for example, Cd, Pr, Nd,etc., and metalloids such as B, P, As, etc. MX_(n) ⁻ is a non-basic,non-nucleophilic anion, such as BF₄ --, PF₆ --, AsF₆ --, SbF₆ --, SbCl₆--, HSO₄ --, ClO₄ --, FeCl₄ ═, SnCl₆ --, BiCl₅ ═, and the like.

Bis-diaryl iodonium salts, such as bis(dodecyl phenyl) iodoniumhexafluoroarsenate and bis(dodecylphenyl) iodonium hexafluoroantimonate,and dialkylphenyl iodonium hexafluoroantimonate are preferred.

Nitrobenzyl sulfonate esters which are useful as photocleavable acids inthe compositions of the present invention have the general formula##STR9## wherein Z is selected from the group consisting of alkylgroups, aryl groups, alkylaryl groups, halogen substituted alkyl groups,halogen substituted aryl groups, halogen substituted alkylaryl groups,nitro substituted aryl groups, nitro substituted alkylaryl groups, arylgroups having nitro and halogen substituents, alkylaryl groups havingnitro and halogen substituents, and a group having the formula C₆ H₄ SO₃CHR'C₆ H_(4-n) Q_(m) (NO)₂, R' is selected from the group consisting ofhydrogen, methyl, and nitro substituted aryl groups, each Q isindependently selected from the group consisting of hydrocarbon groups,hydrocarbonoxy groups, NO₂, halogen atoms, and organosilicon compounds,m has a value of 0, 1, or 2, with the proviso that Q is not an acidicgroup. These nitrobenzyl sulfonate photocleavable acids are described incopending U.S. application for patent, Ser. No. 976,111, filed Nov. 13,1992, which is incorporated herein by reference. A preferred nitrobenzylderivative for the process of the present invention is where m has avalue of 1, Q denotes a NO₂ group in the ortho position in relation tothe --CHR'OS(O)₂ Z group, and Z denotes a nitrophenyl group, wherein thenitro group is in the para position relative to the sulphonic group, orZ denotes a phenylmethyl group, or a trifluoropropylmethylphenyl group.

It is preferred for purposes of this invention that from 90 to 99.9weight percent of the random siloxane copolymer be used in thecompositions of the invention, and it is highly preferred that from 97to 99 weight percent of this composition be employed, said weightpercent being based on the total weight of the composition.

The photocleavable acids may be present in any proportions which effectcuring in the process of this invention. For purposes of the presentinvention, preferably the amount of photocleavable acid is from .1 to 10percent by weight based on the total weight of the composition, and itis highly preferred to use between 1 and 5 percent by weight based onthe total weight of the composition.

The present invention further relates to a method of making a curablecomposition comprising the steps of (I) applying a compositioncomprising (a) a random siloxane polymer and (b) a photocleavable acidto a solid substrate to form a coating, and (II) exposing the coating toan energy source selected from the group consisting of (i) actinicradiation and (ii) actinic radiation in combination with heat in anamount sufficient to cure the coating. The random siloxane polymer andphotocleavable acid are as delineated above for the compositions of thepresent invention including preferred embodiments thereof.

In a preferred embodiment of the instant process the solid substrate isa flexible sheet material such as paper, polyolefin film andpolyolefin-coated paper or foil. Other suitable solid substrates thatcan be coated by the process of this invention include other cellulosicmaterials such as wood, cardboard and cotton; metallic materials such asaluminum, copper, steel and silver; siliceous materials such as glassand stone; and synthetic polymer materials such as polyolefins,polyamides, polyesters and polyacrylates. As to form, the solidsubstrate can be substantially sheet-like, such as a peelable releaseliner for pressure sensitive adhesive; a fabric or a foil; orsubstantially three-dimensional in form.

Step (II) in this method of the present invention comprises exposing thecoating to an energy source selected from the group consisting of (i)actinic radiation and (ii) actinic radiation in combination with heat inan amount sufficient to cure the coating. By actinic radiation it ismeant ultraviolet light; electron beam radiation; and alpha-, beta-,gamma- and x-rays. By heat it is meant infrared radiation, hot-air,microwave radiation, etc. Of course actinic radiation is frequentlyaccompanied by heat and the use of a combination of the two falls withinthe scope and spirit of the present invention.

Herein the term "cure", as applied to the compositions and processes ofthis invention , generally denotes a chemical change which leads to achange in the state of the composition from a liquid to a solid. Curingitself may be achieved in any of the known ways, including passing acoated substrate under the desired source of radiation, for example a UVlamp, at a predetermined rate and exposing a completely coated substrateto radiation by switching on the required energy source for apredetermined time.

In a preferred embodiment of the process of this invention, a flexiblesheet material, such as paper, metal foil or tapestock, is coated with athin coating of the liquid curable composition, preferably in acontinuous manner and the thus-coated material is then heated and/orirradiated to rapidly cure the coating, to provide a sheetlike materialbearing on at least one surface thereof an adhesive-releasing coating.The adhesive-releasing coating is subsequently brought into contact witha pressure sensitive adhesive, preferably in an in-line manner, to forman article having a peelable, i.e. releasable, adhesive/coatinginterface. Examples of such an article include, adhesive labels having apeelable backing, adhesive tape in roll form and adhesive packaged in astrippable container. The pressure sensitive adhesive can benon-silicone-based, such as the well-known acrylic or rubber types orsilicone-based, such as the peroxide- or platinum-curablepolydiorganosiloxane-based adhesives.

The methods and compositions of this invention are also applicable toadhesive materials other than pressure sensitive adhesives. Examples ofsaid adhesive materials include foods, asphalt and gum polymers. Thecompositions of the present invention are useful as release coatings forpressure sensitive adhesives, as protective coatings and decorativecoatings.

The compositions prepared in the method and process of this inventionand the curable coating compositions of this invention can contain anyoptional components such as photosensitizers, high release additives,reinforcing and extending fillers, hydrocarbons and halohydrocarbons,colorants, dyes, preservatives, fragrances, stabilizers, adhesionmodifiers, adhesive-release modifiers, diluents, etc.

The method and process of this invention can be completed by mixing thematerials described hereinabove and any optional components in the orderdelineated above, using any suitable mixing means, such as a spatula, adrum roller, a mechanical stirrer, a three-roll mill, a sigma blademixer, a bread dough mixer, and a two-roll mill. In the process of thisinvention, the coating method can be accomplished by any suitable mannerknown in the art, such as by spreading, brushing, extruding, spraying,gravure, kiss-roll and air-knife.

The following examples are disclosed to further teach, but not limit,the invention which is properly delineated by the appended claims. Allamounts (parts and percentages) are by weight unless otherwiseindicated. The structures presented in the examples are expressed inmole percents unless otherwise indicated.

Cure time for a composition means the time interval required for thecomposition, when coated onto S2S kraft paper or polypropylene-film, ata thickness of 1 pound silicone per ream of paper or film, to attain theno smear, no migration, no rub-off condition.

The no smear condition was determined by lightly streaking the coatingwith a finger and observing for the absence of haze in the streakedarea.

The no migration condition was determined by firmly adhering a common,pressure sensitive adhesive tape to the coating, removing the tape andfolding the removed tape together, adhesive surfaces to each other.Absence of migration of the coating to the tape was indicated by notingthat the doubled tape was as difficult to separate as unused tape sodoubled.

The no rub-off condition was determined by vigorously rubbing thecoating with the index finger and noting that the coating could not beremoved from the paper.

RMS(Root Mean Square--i.e. the square root of the arithmetic mean of thesquares of a set of numbers (an average value)) was measured on a highspeed peel tester, and SAS(Subsequent Adhesive Strength) was measured ona low speed peel tester.

EXAMPLE 1

A 3-neck 100 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 10.95 g (0.0805moles) MeSi(OMe)₃, 53.62 g (0.7246 moles) (Me₂ SiO)_(x), 10.36 g (0.0893moles) hydroxybutylvinylether and 0.124 g potassium silanolate (1500NE(Neutralization Equivalent)). The flask was heated to 130° C. for 4hours during which time methanol by-product was taken off. After coolingto room temperature, 0.0074 g (0.12 mmoles) glacial acetic acid wasadded and the mixture stirred 24 hours. The reaction product wasfiltered through diatomaceous earth and then stripped at 128° C./1 mm Hgfor 1 hour. The composition produced had the following average structure##STR10##

EXAMPLE 2

A 3-neck 100 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 8.87 g (0.0652moles) MeSi(OMe)₃, 43.43 g (0.5869 moles) (Me₂ SiO)_(x), 22.71 g (0.1958moles) hydroxybutylvinylether and 0.1 g potassium silanolate (1500 NE).The flask was heated to 130° C. for 4 hours during which time methanolby-product was taken off. After cooling to room temperature, 0.0060 g(0.10 mmoles) glacial acetic acid was added and the mixture stirred 16hours. The reaction product was filtered through diatomaceous earth andthen stripped at 125 C/1 mm Hg for 2 hours. The composition produced hadthe following average structure ##STR11##

EXAMPLE 3

A 3-neck 100 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 2.09 g (0.0154moles) MeSi(OMe)₃, 67.64g (0.9140 moles) (Me₂ SiO)_(x), 5.36 g (0.0462moles) hydroxybutylvinylether and 0.134 g potassium silanolate (1500NE). The flask was heated to 130° C. for 4 hours during which timemethanol by-product was taken off. After cooling to room temperature,0.0080 g (0.134 mmoles) glacial acetic acid was added and the mixturestirred 16 hours. The reaction product was filtered through diatomaceousearth and then stripped at 117 C/1 mm Hg for 1 hour. The compositionproduced had the following average structure ##STR12##

EXAMPLE 4

A 3-neck 100 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 74.03 g (1.0 mole)(Me₂ SiO)_(x) and 2.31 g (0.02 moles) hydroxybutylvinylether. The flaskwas heated to 130° C. and then 0.14 g potassium silanolate (1500 NE)added. Heating was continued for 4 hours. After cooling to roomtemperature, 0.0085 g (0.14 mmoles) glacial acetic acid was added andthe mixture stirred 5 hours. The reaction product was filtered throughdiatomaceous earth and then stripped at 125 C/1 mm Hg for 11/2 hours.The composition produced had the following average structure (in moles):

    Me.sub.2 (ViOBuO)SiO(Me.sub.2 SiO).sub.163 SiMe.sub.2 (OBuOVi)

EXAMPLE 5

A 3-neck 2 liter flask equipped with a thermometer, water condenser,mechanical stirrer and 500 ml dropping funnel was charged with 899.8 g(6.616 moles) MeSi(OMe)₃ and 5.91 g (0.162 moles) concentrated HCl. Theflask was heated to 60° C. and then 113.56 g (6.309 moles) H₂ O and267.98 g (8.37 moles) MeOH added via dropping funnel over the course of1 hour, maintaining a pot temperature of 65°-70° C. by the rate of H₂O/MeOH addition. After refluxing 31/2 hours, the flask was heated to130° C., allowing 744 g volatiles to be taken off (strongly acidic). Theacid number of the product was measured to be 0.2. Next, 2.2 g (0.026mole) NaHCO₃ and 2.2 g diatomaceous earth were added to the product inthe flask and the mixture stirred at room temperature 64 hours. Theproduct was then pressure filtered. Acid number was measured to be lessthan 0.0002. The composition produced had the following averagestructure ##STR13##

EXAMPLE 6

A 3-neck 50 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 14.89 g fluid fromExample 5, 4.87 g (0.0420 moles) hydroxybutylvinylether and 0.2 g(0.0022 moles) tetraisopropyltitanate. The flask was heated to 85° C.for 4 hours during which time methanol by-product was taken off. Thecomposition produced had the following average structure ##STR14##

EXAMPLE 7

A 3-neck 50 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 14.89 g fluid fromExample 5, 7.31 g (0.0630 moles) hydroxybutylvinylether and 0.22 g(0.0024 moles) tetraisopropyltitanate. The flask was heated to 85° C.for 4 hours during which time methanol by-product was taken off. Thecomposition produced had the following average structure ##STR15##

EXAMPLE 8

A 3-neck 50 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 14.89 g fluid fromExample 5, 9.76 g (0.0841 moles) hydroxybutylvinylether and 0.25 g(0.0028 moles) tetraisopropyltitanate. The flask was heated to 85° C.for 7 hours during which time methanol by-product was taken off. Thecomposition produced had the following average structure ##STR16##

EXAMPLE 9

A 3-neck 50 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 14.89 g fluid fromExample 5, 12.20 g (0.1052 moles) hydroxybutylvinylether and 0.26 g(0.0028 moles) tetraisopropyltitanate. The flask was heated to 85° C.for 14 hours during which time methanol by-product was taken off. Thecomposition produced had the following average structure ##STR17##

EXAMPLE 10

A 3-neck 50 ml flask equipped with a thermometer, magnetic stirrer,short path still, and nitrogen purge was charged with 14.89 g fluid fromExample 5, 7.31 g (0.0630 moles) hydroxybutylvinylether and 0.21 g(0.0011 moles) barium hydroxide monohydrate. The flask was heated to 85°C. for 5 hours during which time methanol by-product was taken off.Product was then pressure filtered. The composition produced had thefollowing average structure ##STR18##

The following examples illustrate the effectiveness of the compositionsof the present invention as release coatings.

EXAMPLE 11

The fluid of Example 1 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to 1556 mJ/cm² UV light and produced a clear,smooth coating with no rub off and no migration.

EXAMPLE 12

The fluid of Example 2 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to 835 mJ/cm² UV light and producted a clear,smooth coating with no rub off and no migration.

EXAMPLE 13

The fluid of Example 6 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to 312 mJ/cm² UV light and cured atapproximately 125 ft/min using Fusion 600 Watt/inch H Bulb with no ruboff and no migration.

EXAMPLE 14

The fluid of Example 7 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to less than 80 mJ/cm² UV light and cured atapproximately 375 ft/min using Fusion 600 Watt/inch H Bulb with no ruboff and no migration. Coated sheet was clear, smooth, with no odor.

EXAMPLE 15

The fluid of Example 8 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to 96 mJ/cm² UV light and cured atapproximately 290 ft/min using Fusion 600 Watt/inch H Bulb with no ruboff and no migration. Coated sheet was clear, smooth, with no odor.

EXAMPLE 16

The fluid of Example 8 was also evaluated for release against TESA 7475(acrylic tape) and TESA 7476 (rubber tape) at 400 inches per minute.Release was evaluated at two different cure levels, 125 ft/min and 375ft/min. The results are recorded in Table I below.

                  TABLE I                                                         ______________________________________                                        Tape      Cure speed                                                                              Release    RMS*  SAS**                                    ______________________________________                                        TESA 7475 125 ft/min                                                                              131.8 g/in 132.3 83.3                                     TESA 7475 375 ft/min                                                                              212.1 g/in 221.5 87.5                                     TESA 7476 125 ft/min                                                                              121.9 g/in 148.5 54.9                                     TESA 7476 375 ft/min                                                                              166.1 g/in 184.6 48.7                                     ______________________________________                                         *Root mean square, measured on high speed peel tester (Zpe 1.21)              **Subsequent adhesive strength, measured on low speed peel tester        

EXAMPLE 17

The fluid of Example 9 was coated on biaxially orientated polypropylenewith 2 wt % bisdodecylphenyl iodonium hexafluoroantimonate catalyst. Thecoated surface was exposed to less than 88 mJ/cm² UV light and cured atapproximately 325 ft/min using Fusion 600 Watt/inch H Bulb with no ruboff and no migration.

EXAMPLE 18

A three neck flask equipped with a mechanical stirrer, heating mantle,thermometer and condenser was loaded with 75 gms (4.17 moles) of H₂ O,74.88 gms (0.36 moles) of Si(OCH₂ CH₃)₄, and 9.98 gms (0.086 moles) ofHOCH₂ CH₂ CH₂ CH₂ OCH═CH₂. The flask was heated to 60° C with agitation.1.30 gms (0.0074 moles) of NH₄ OH as a 20% by weight aqueous solutionwas added and heating maintained for 35 minutes. After 35 minutes 200gms (1.24 moles) of (Me₃ Si)₂ NH was added slowly. Heating wasmaintained for an hour. Transferred to a separatory funnel andneutralized by washing several times with water. To aid in separation 80gms (0.8 moles) of n-heptane was added during the final wash. Theheptane resin layer was added to a flask and the heptane stipped offusing a rotoevaporator. The product was a clear liquid resin.

EXAMPLE 19

The procedure of Example 18 was repeated the only difference was that89.44 (0.43 moles) of Si(OCH₂ CH₃)₄ was used instead of 78.44 gms (0.36moles) and 90 gms (5.00 moles) of water. All other ratios were the same.The composition produced was a resin.

EXAMPLE 20

The resin of example 18 was was mixed with 2.0% by weight ofbisdodecylphenyl iodonium hexafluoroantimonate catalyst and coated atapproximately 1 micron thickness. Cure to no migration was accomplishedafter exposure to 963 mJ/cm² irradiation from a fusion UV processorequipped with a 600 Watt H bulb.

EXAMPLE 21

The resin of example 19 was mixed with 2.0 % by weight ofbisdodecylphenyl iodonium hexafluoroantimonate catalyst and coated atapproximately 1 micron thickness. Cure to no migration was accomplishedafter exposure to 1174 mJ/cm² irradiation from a fusion UV processorequipped with a 600 H bulb.

Table II shown hereinbelow indicates the range of values of w, x, y, andz (in mole percents) in the compositions of the present inventionproduced by the methods of the present invention. The compositions ofthe present invention have the general formula: ##STR19##

                                      TABLE II                                    __________________________________________________________________________    Ex. 1                                                                              Ex. 2                                                                            Ex. 3                                                                            Ex. 4                                                                             Ex. 6                                                                            Ex. 7                                                                            Ex. 8                                                                            Ex. 9                                                                            Ex. 10                                                                            Ex. 18                                                                            Ex. 19                                     Mole Percent                                                                  __________________________________________________________________________    w 19.0                                                                             23.9                                                                             5.0                                                                              0.012                                                                             21.7                                                                             19.5                                                                             23.1                                                                             15.2                                                                             22.4                                                                              22.50                                                                             25.75                                      x 72.2                                                                             67.1                                                                             93.5                                                                             99.988                                                                            54 54.3                                                                             51.4                                                                             50.2                                                                             47.4                                                                              0   0                                          y 8.8                                                                              9.0                                                                              1.5                                                                              0   24.3                                                                             26.2                                                                             25.5                                                                             34.6                                                                             30.2                                                                              0   0                                          z 0  0  0  0   0  0  0  0  0   77.50                                                                             74.25                                      __________________________________________________________________________

It should be apparent from the foregoing that many other variations andmodifications may be made in the compounds, compositions and methodsdescribed herein without departing substantially from the essentialfeatures and concepts of the present invention. Accordingly it should beclearly understood that the forms of the invention described herein areexemplary only and are not intended as limitations on the scope of thepresent invention as defined in the appended claims.

That which is claimed is:
 1. A method of making a vinylether functionalsiloxane, the method comprising the steps of:(I) reacting:(a) a silanehaving the formula R_(x) Si(OR¹)_(4-x) ; (b) water; (c) a non-acidiccondensation catalyst selected from the group consisting of aminecarboxylates, heavy metal carboxylates, isocyanates, silanolates,phenoxides, mercaptides, CaO, BaO, LIOH, BuLi, amines, and ammoniumhydroxides; (d) a vinyl ether compound having the formula HOR² OCH═CH₂wherein R is a monovalent hydrocarbon or halohydrocarbon radical havingfrom 1 to 20 carbon atoms, R¹ is a monovalent alkyl radical having from1 to 8 carbon atoms, R² is a divalent hydrocarbon or halohydrocarbonradical having from 1 to 20 carbon atoms x has a value of from 0 to 3,with the proviso that the molar ratio of water to alkoxy radicals isless than 0.5; (II) removing alcohol from the mixture of (I); (III)neutralizing the mixture of (II); (IV) adding a transesterificationcatalyst to the mixture of (III); and (V) removing volatiles from themixture of (IV).
 2. A method according to claim 1, further comprisingadding an endcapping agent prior to step (III).
 3. A method according toclaim 1, further comprising heating the mixture after step (I).
 4. Amethod according to claim 1, further comprising adding apolydiorganosiloxane having the formula

    HOSiR.sup.4.sub.2 (R.sup.4.sub.2 SiO).sub.n OSiR.sup.4.sub.2 OH

wherein R⁴ is selected from the group consisting of a monovalenthydrocarbon radical or halohydrocarbon radical having from 1 to 20carbon atoms, and n has a value of 0 to 15,000, prior to step (III). 5.A method according to claim 1, wherein (c) is selected from the groupconsisting of silanolates and ammonium hydroxides.
 6. A method accordingto claim 1, wherein the transesterification catalyst is selected fromthe group consisting of dimethyltin neodecanoate, dibutyltin diacetate,dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, zincnapthenate, cobalt napthenate, zinc octylate, tin octylate, cobaltoctylate, diisooctyl mercaptoacetate, zirconium napthenate, zirconiumoctylate, tetrabutyl orthotitanate, tetraisopropyl titanate, bariumhydroxide monohydrate, and stannous octoate.
 7. A method according toclaim 1, wherein the transesterification catalyst is selected the groupconsisting of tetraisopropyl titanate, barium hydroxide monohydrate, andsodium methoxide.
 8. A method of making a vinylether functionalsiloxane, the method comprising the steps of:(I) reacting in thepresence of a non-acidic equilibration catalyst selected from the groupconsisting of amine carboxylates, heavy metal carboxylates, isocyanates,silanolates, phenoxides, mercaptides, CaO, BaO, LiOH, BuLi, amines,potassium hydroxides, cesium hydroxides, ammonium hydroxides, andphosphorus hydroxides:(a) a cyclic compound having the formula:##STR20## with (b) a compound having the formula HOR⁶ OCH═CH₂ wherein R⁵is a monovalent hydrocarbon radical or halohydrocarbon radical havingfrom 1 to 20 carbon atoms, R⁶ is a divalent hydrocarbon orhalohydrocarbon radical having from 1 to 20 carbon atoms, and y has avalue of from 3 to 10; (II) removing volatiles from the mixture of (I);and (III) neutralizing the mixture of (II).
 9. A method according toclaim 8, further comprising heating the mixture after step (I).
 10. Amethod according to claim 8, the method further comprising adding apolydiorganosiloxane having the formula

    HOSiR.sup.7.sub.2 (R.sup.7.sub.2 SiO).sub.n OSiR.sup.7.sub.2 OH

wherein R⁷ is a monovalent hydrocarbon radical or halohydrocarbonradical having from 1 to 20 carbon atoms, and n has a value of 0 to15,000, prior to step (III).
 11. A method according to claim 8, themethod further comprising adding a silane having the formula R⁸ _(x)Si(OR⁹)_(4-x) prior to step (III), wherein R⁸ is a monovalenthydrocarbon or halohydrocarbon radical having from 1 to 20 carbon atoms,R⁹ is a monovalent alkyl radical having from 1 to 8 carbon atoms, x hasa value of from 0 to
 3. 12. A composition produced in accordance withthe method of claim
 8. 13. A method according to claim 8, wherein thenon-acidic equilibration catalyst is selected from the group consistingof potassium silanolates and sodium silanolates.